Sustained-release thermoplastic polymer composition and product comprising the same

ABSTRACT

The polymer composition comprises a polymer and a liquid compound having poor compatibility with the polymer. When the liquid compound is caused to be held in the polymer in a high concentration, a block copolymer having in the molecule a copolymerized polymer block unit having high compatibility with both of the matrix polymer and the liquid compound is incorporated and dispersed. As a result, the block copolymer serves like a surfactant to form an interface and the liquid compound is enclosed inside the interface to thereby form a liquid-in-solid polymer type emulsion.

This application is a divisional of U.S. patent application Ser. No.11/993,220 filed on Dec. 19, 2007, which claims priority based uponInternational Patent Application No. PCT/JP2006/313824 filed on Jul. 12,2006, all of which are hereby incorporated by reference in theirentirety.

TECHNICAL FIELD

The present invention relates to a sustained-release polymer compositioncontaining a functional liquid compound, rapid bleeding of which issuppressed and which is sustainedly released such that the function ofthe liquid compound can last for a long period of time, and to a productformed from the composition.

BACKGROUND ART

In production of a molded article, such as a film, a sheet, a bottle ora fiber, made from a thermoplastic polymer as a raw material, the moldedarticle is produced by adding to the material a functional organiccompound such as an antioxidant, a thermal stabilizer, an ultravioletray absorbing agent or an antistatic agent and so on, and forming themixture with a method such as an extrusion molding, a blow molding or aninjection molding. Moreover, a molded product has been investigatedwhich expresses a function by containing a functional compound, e.g., anodorous substance, an insecticide, a repellant or an antibacterialcompound in a molded product and sustainedly releasing the functionalcompound from the molded product.

However, except for a plasticizer for vinyl chloride resin or a specialexample (Patent Document 1) in which an ethylene-vinyl acetate copolymeris swelled and contained with a solvent at a room temperature, a contentof a liquid at a room temperature is remarkably small. As a compoundother than the above examples, a liquid compound content, which can becontained in a general thermoplastic polymer, is limited in a rangewithout a practical problem. And the state of such a liquid compound isnot a droplet. Moreover, since the liquid compound is forcedly confinedin the polymer as a phase separation state by melt-kneading process orothers, the compound has no practical use because of a large amount ofbleeding it out on a surface in a short period of time. On the otherhand, a matter which contains a low content of a liquid compounddisappears the liquid compound in such a short period of time as severalweeks at most, and lacks a long-term duration of the function.

In order to aid diffusion of a volatile component to a surface, there isan example (Patent Document 2) which adds a hydrogenated diene-seriespolymer to a polypropylene to sustainedly release the volatilecomponent. However, it is the self-evident truth that a disappearentrate of the volatile component increases as a diffusion rate is larger.Therefore, the above example is contradictory and is a theoreticallyimpracticable proposal. Moreover, in the proposal, there is nodescription that the volatile component stably exists in the form of aliquid in a matrix polymer, and no description about compatibilitybetween the additive and the matrix polymer at all.

A paint (or coating) includes a powdered paint and a liquid paint. As apowder coating for a thin film having about 50 μm, there areelectrostatic spraying methods such as a corona system and a tribosystem. In the corona system, a powder is electrostatically attached toa coated object by applying a high voltage (30-90 KV) on a corona pinprovided with a tip of a gun for spraying the powder, and charging thepowder (paint) released in the electric field between the pin and theobject. In the tribo system, a powder is attached to a coated object bygenerating electrostatic charges with the friction between an inner wallof a gun and the powder when the powder passes through the inside of thegun.

A coated object to which a powdered paint is attached is baked in afurnace at 150 to 200° C. for 10 to 20 minutes so that the coating isfinished. As a polymer component in the paint, thermoplastic andthermosetting polymers are used. The thermosetting polymer is oftenmodified in an end thereof to enable combination use with a curing agentsuch as a urethane or epoxy curing agent.

As a powder coating method for coating a thick film, there are afluidized bed coating method and an electrostatic spraying method. Inthe fluidized bed coating method a thermoplastic powdered paint ismainly used, and in an electrostatic spraying method a thermosettingpowdered paint is mainly used. The fluidized bed coating methodcomprises suspending and floating of a powdered paint by a compressedair, and dipping of a pre-heated object to be coated in the floatingpaint. In this method, the floating paint is fused and adhered to theobject to usually give a thick paint film by 200 to 500 μm thickness.The polymer for the thermoplastic powdered paint used in the fluidizedbed coating method may include, for example, a polyvinyl chloride, apolyethylene, a polypropylene, a polyester, a nylon, and so on.

The generally used liquid paint is provided in an aqueous type and asolvent type. To such a liquid paint are blended a pigment, a dispersingagent (or dispersant), a stabilizer, a polymer, a crosslinking agent andothers. The thickness of the film is 15 to 60 μm. Out of considerationto the environment, use of the aqueous type paint has increased. As thepolymer to be blended, a thermoplastic or thermosetting polymer is used.For example, the polymer includes an alkyd polymer, an unsaturatedpolyester-series polymer, an epoxy-series polymer, a melamine-seriespolymer, an acrylic resin, a urethane-series polymer, a phenol-seriespolymer, a nylon-series polymer, an ester-series polymer, and afluorocarbon resin.

The ship's bottom encrusted and fouled with extraneous matters such as abarnacle and so on increases friction with water, and is not economicalin the running. For example, it has been suggested that an organic tincompound, copper oxide, mercury oxide, and others are used as anantifouling agent (Patent Documents 3 and 4). Moreover, in order toimpart an antifouling property to a ship's bottom paint, an organic tincompound has been used by being mixed with the paint. However, since ithas been known that an organic tin acts as an endocrine-disruptingchemical, such a compound has dropped out of use. Moreover, copper oxideand mercury oxide are also highly toxic compounds. On the other hand,many self polishing-type ship's bottom paints are commerciallyavailable. In these paints, it is considered that a fresh layer of thepaint is constantly exposed by peeling off of the paint in the surfacelayer due to hydrolysis of the paint polymer, and decrease in thethickness of the paint film. However, since the ship's bottom isencrusted with the fouling matter until the surface layer peels off, itis inevitable that the effect of the paint is limited.

A highly safe antifouling agent may include an essential oil. Theessential oil has been also used as a food additive over the yearsbefore Christ. However, the essential oil has intractability due tovolatility. As a method for mixing a polymer and a volatile compound,there is a method which comprises allowing a porous powder such as arubber component or a zeolite to contain a volatile component inadvance, and mixing the resulting matter and the polymer temporarily.However, in such a method, although the polymer was temporarily allowedto contain the volatile component at a high concentration, it wasdifficult to sustainedly release the volatile component over a longperiod of time because of fast diffusion (or spread) of the volatilecomponent. Further, the method had a shortcoming of increasing thediffusion rate as the surface area increases. Therefore, in a paintapplication for coating a large surface area with a thin film, thediffusion of the volatile component was fast.

Moreover, as an example for using a polymer having thermoplasticity inspite of containing water, there has been proposed a method whichcomprises mixing and allowing an inorganic substance (e.g., magnesiumhydroxide, aluminum hydroxide and calcium silicate) to contain in thepolymer, wherein the inorganic substance is in the form of a hydratestate (or has crystallization water) (Patent Document 5). However, sincethe crystallization water of the inorganic substance is released at atemperature as relatively high as 300 to 550° C., the method isdisadvantageous in that the crystallization water does not act at a lowtemperature. It is impossible to allow the crystallization water tocontain a solute therein.

Further, as a filter used for the purpose of dust collection, there isused a fabric such as a textile (a woven or knitted cloth) or a nonwovenfabric, a three-dimensionally assembled fiber structure, and others. Thefilter is considered to have higher performance as the filter has lowerpressure loss and higher dust collection efficiency. In general,improvement of dust collection efficiency can be achieved to some extentby increasing a fiber density in the fabric or fiber structure, whilethe high fiber density results in a lower air permeability. Therefore,in order to ensure the air permeability in excess of a certain level tofunction as a filter, the dust collection efficiency is restricted.

In order to improve the dust collection efficiency while ensuring theair permeability in excess of a certain level, it is effective that thediameter of the fiber constituting the filter is small, and variousfilters using an ultra-fine fiber have been proposed. Moreover, it isalso utilized to collect dust by electrostatic force. There has beenutilized a meltblown nonwoven fabric made from an ultra-fine fiber,which is subjected to electreting for collecting dust throughelectrostatic induction by electrizing a filter itself. However, thiselectreting tends to neutralize the effect after exposure under a hightemperature not lower than 50° C. or after a long time. Therefore, thefilter had a propensity to be lack of washing resistance and durability.

Moreover, a method of collecting dust by a scrubber for water sprinklinghas been also generally used. For example, a method for collecting dustby combination of a bag filter and a scrubber has been adopted for anincinerator flue gas. In a fine particle having a particle size of notlarger than several micrometers, generally, a liquid bridging force ismore dominant than an electrostatic force for the adherence of the fineparticles. Thus, the scrubber utilizes effective collection of the fineparticle due to the liquid bridging force of water.

As an example that the liquid bridging force is utilized for a filteritself, there is utilized a filter improved in a dust collectionefficiency thereof, which comprises a fiber structure impregnated with alow-volatile oil component, wherein the fiber structure comprises staplefibers entangled by needle punch or others. However, the filter islimited to such a loose clearance one having a high air permeabilitythat the oil component to be impregnated does not inhibit the airpermeability.

Moreover, a fabric for a clean room wear has been proposed whichcomprises a fiber made from a polymer having a hydrous inorganiccompound kneaded therein and has an improved dust collection efficiencywith maintaining a relatively high air permeability by slightly coatingthe surface of the fiber with water (Patent Document 6). However, thehigh dust collection efficiency is limited to the case of an air flowrate as low as 0.09 cm/second. Therefore, in the case of a commonly usedair filter having an air flow rate of 5 to 8 cm/second, an excellentdust collection efficiency cannot be expressed.

Patent Document 1: Japanese Patent Application Laid-Open No. S58-12654

Patent Document 2: Japanese Patent Application Laid-Open No. H10-87920

Patent Document 3: Japanese Patent Application Laid-Open No. S49-53924

Patent Document 4: Japanese Patent Application Laid-Open No. S49-92178

Patent Document 5: Japanese Patent Application Laid-Open No. H06-316031

Patent Document 6: Japanese Patent Application Laid-Open No. 2004-360161

DISCLOSURE OF INVENTION Problems to be Solved by the Invention

In mixing a polymer and a liquid compound having a low compatibilitywith the polymer, a large amount of the liquid compound bleeds out froma surface of a product thereof. Therefore, it is practically difficultto mix the polymer and the liquid compound. Moreover, in the case wherea large amount of the liquid compound having the low compatibilitybleeds out in a short period of time, the duration of the effect isinsufficient. A problem of the invention is to provide asustained-release polymer composition which ensures a long-term durationof the function by enabling to add to a polymer a liquid compound havinga low compatibility with the polymer at a high concentration in a stablestate, and sustainedly releasing the compound over a long period oftime; and a product therefrom.

Means for Solving the Problems

According to a composition of the present invention, to retain a liquidcompound having low compatibility with polymers with a highconcentration, a block copolymer which contains a matrix polymer, theliquid compound, and a polymer unit highly compatible with the matrixpolymer and the liquid compound in the form of block copolymerization inone molecule is blended and dispersed. The block copolymer functions ina surfactant-like fashion to form an interface, in which emulsioncontaining the liquid compound therein is formed. Herein, thecomposition of the present invention is referred to as “liquid-in-solidpolymer emulsion”.

The present invention is directed to a composition which constitutes aliquid-in-solid polymer emulsion at room temperature, including: athermoplastic polymer (A); 0.1 to 50 parts by weight of a blockcopolymer (B) mixed with 100 parts by weight of the thermoplasticpolymer (A), the block copolymer (B) being phase-separated from thethermoplastic polymer (A); and 0.1 to 20 parts by weight of a liquidcompound (C) dispersed in 100 parts by weight of the mixture of thethermoplastic polymer (A) and the block copolymer (B), wherein the blockcopolymer (B) contains a block (b1) having high compatibility with thethermoplastic polymer (A) but low compatibility with the liquid compound(C) and a block (b2) having high compatibility with the liquid compound(C) but low compatibility with the thermoplastic polymer (A), the liquidcompound (C) has low compatibility with the block (b1) and thethermoplastic polymer (A) but high compatibility with the block (b2),the liquid compound (C) being phase-separated from the thermoplasticpolymer (A) and being liquid at 100° C. or lower, the liquid compound(C) is enclosed by the block copolymer (B) by a surfactant-like functionof the block copolymer (B), the thermoplastic polymer (A) is apolyolefin polymer, the block (b1) is a polyolefin block and the block(b2) is a polystyrene block, and the block copolymer (B) is at least oneselected from the group consisting of apolystyrene-poly(ethylene/propylene) block copolymer, apolystyrene-poly(ethylene/butylene) block copolymer, apolystyrene-poly(ethylene/propylene)-polystyrene block copolymer, apolystyrene-poly(ethylene/butylene)-polystyrene block copolymer, and apolystyrene-poly(ethylene-ethylene/propylene)-polystyrene blockcopolymer. Hereinafter, this composition is sometimes referred to as“Composition (I)”.

The present invention is also directed to another composition whichconstitutes a liquid-in-solid polymer emulsion at room temperature,including: a thermoplastic polymer (A); 0.1 to 50 parts by weight of ablock copolymer (B) mixed with 100 parts by weight of the thermoplasticpolymer (A), the block copolymer (B) being phase-separated from thethermoplastic polymer (A); and 0.1 to 20 parts by weight of a liquidcompound (C) dispersed in 100 parts by weight of the mixture of thethermoplastic polymer (A) and the block copolymer (B), wherein the blockcopolymer (B) contains a block (b1) having high compatibility with thethermoplastic polymer (A) but low compatibility with the liquid compound(C) and a block (b2) having high compatibility with the liquid compound(C) but low compatibility with the thermoplastic polymer (A), the liquidcompound (C) has low compatibility with the block (b1) and thethermoplastic polymer (A) but high compatibility with the block (b2),the liquid compound (C) being phase-separated from the thermoplasticpolymer (A) and being liquid at 100° C. or lower, the liquid compound(C) is enclosed by the block copolymer (B) by a surfactant-like functionof the block copolymer (B), the thermoplastic polymer (A) is apolystyrene polymer, the block (b1) is a polystyrene block and the block(b2) is a polyolefin block, and the block copolymer (B) is at least oneselected from the group consisting of apolystyrene-poly(ethylene/propylene) block copolymer, apolystyrene-poly(ethylene/butylene) block copolymer, apolystyrene-poly(ethylene/propylene)-polystyrene block copolymer, apolystyrene-poly(ethylene/butylene)-polystyrene block copolymer, and apolystyrene-poly(ethylene-ethylene/propylene)-polystyrene blockcopolymer. Hereinafter, this composition is sometimes referred to as“Composition (II)”.

EFFECTS OF THE INVENTION

The present invention relates to a sustained-release compositioncontaining a liquid compound which is liquid at 100° C. or lower, rapidbleeding of which is suppressed and which is sustainedly released suchthat the function of the liquid compound can last for a long period oftime, and to a product formed from the composition.

Compositions of the present invention are used as materials for, forexample, extrusion-molded articles, injection-molded articles, androtational-molded articles, such as a fiber, a fabric or fiber productmade of the fiber, a coating material, a covering material, paint, apipe, a sheet, a film, and a laminate product, etc. The compositions ofthe present invention may contain, as the liquid compound, apharmaceutical product, an antibacterial agent, an antifungal agent, anantiviral agent, an antistatic agent, an antialgal agent, apreservative, an aromatic agent, an insect repellent, an insecticide, arodent repellent, a bird repellent, an animal repellent, an attractant,an agricultural chemical, an antifouling agent, a flame retardant, adust-capturing agent, a fertilizer, or a deodorant, in which thefunction of the liquid compound can be sustained for several years.Further, according to the present invention, it is possible to form anextremely thin liquid coating having a thickness of 1 μm or less. Thecompositions of the present invention are also used for a high functionfilter which includes as a main dust-capturing material such fabric andfiber product, and a laminate thereof.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a scanning electron microphotograph of dispersed pellets(masterbatch) prepared in Example 1.

FIG. 2 is a scanning electron microphotograph of dispersed pellets(masterbatch) prepared in Example 2.

FIG. 3 is a scanning electron microphotograph of dispersed pellets(masterbatch) prepared in Example 3.

FIG. 4 is a scanning electron microphotograph showing a cross section ofa multifilament prepared in Example 4.

FIG. 5 is a scanning electron microphotograph of dispersed pellets(masterbatch) prepared in Example 5.

BEST MODE FOR CARRYING OUT THE INVENTION

Compositions (I) and (II) each constitute a liquid-in-solid polymeremulsion at room temperature. The composition includes: a thermoplasticpolymer (A); 0.1 to 50 parts by weight of a block copolymer (B) mixedwith 100 parts by weight of the thermoplastic polymer (A), the blockcopolymer (B) being phase-separated from the thermoplastic polymer (A);and 0.1 to 20 parts by weight of a liquid compound (C) dispersed in 100parts by weight of the mixture of the thermoplastic polymer (A) and theblock copolymer (B), wherein the block copolymer (B) contains a block(b1) having high compatibility with the thermoplastic polymer (A) butlow compatibility with the liquid compound (C) and a block (b2) havinghigh compatibility with the liquid compound (C) but low compatibilitywith the thermoplastic polymer (A), the liquid compound (C) has lowcompatibility with the block (b1) and the thermoplastic polymer (A) buthigh compatibility with the block (b2), the liquid compound (C) beingphase-separated from the thermoplastic polymer (A) and being liquid at100° C. or lower, the liquid compound (C) is enclosed by the blockcopolymer (B) by a surfactant-like function of the block copolymer (B),the thermoplastic polymer (A) is a polyolefin polymer, the block (b1) isa polyolefin block and the block (b2) is a polystyrene block, and theblock copolymer (B) is at least one selected from the group consistingof a polystyrene-poly(ethylene/propylene) block copolymer, apolystyrene-poly(ethylene/butylene) block copolymer, apolystyrene-poly(ethylene/propylene)-polystyrene block copolymer, apolystyrene-poly(ethylene/butylene)-polystyrene block copolymer, and apolystyrene-poly(ethylene-ethylene/propylene)-polystyrene blockcopolymer.

The present invention is also directed to a composition including: adispersion medium; and Composition (I) or (II) constituting aliquid-in-solid polymer emulsion at room temperature which is dispersedin the dispersion medium, wherein the dispersion medium is any one of apolymer other than the thermoplastic polymer (A), a blend of the polymerother than the thermoplastic polymer (A) and a plasticizer, and asolution of the polymer other than the thermoplastic polymer (A).Hereinafter, this composition is sometimes referred to as “Composition(III)”. Also, Compositions (I), (II) and (III) are generically referredto as “composition(s) of the present invention”.

The present invention is directed to Composition (III) wherein thepolymer other than the thermoplastic polymer (A) is a thermoplasticpolymer, a thermosetting polymer or a thermosetting polymer precursor.

The present invention is directed to Compositions (I), (II) and (III)wherein the liquid compound (C) which is liquid at 100° C. or lower isan organic compound or an organic compound solution.

In Composition (I) of the present invention, the thermoplastic polymer(A) is a polyolefin polymer, the block (b1) is a polyolefin block whichhas high compatibility with the polyolefin polymer (thermoplasticpolymer (A)) and the block (b2) is a polystyrene block which has highcompatibility with the liquid compound (C), and the block copolymer (B)is at least one selected from the group consisting of apolystyrene-poly(ethylene/propylene) block copolymer (SEP), apolystyrene-poly(ethylene/butylene) block copolymer (SEB), apolystyrene-poly(ethylene/propylene)-polystyrene block copolymer (SEPS),a polystyrene-poly(ethylene/butylene)-polystyrene block copolymer(SEBS), and a polystyrene-poly(ethylene-ethylene/propylene)-polystyreneblock copolymer (SEEPS).

In Composition (I) of the present invention, the liquid compound (C) isan organic compound or organic compound solution including an aromaticring, alicyclic skeleton or polar group which has higher compatibilitywith polystyrene than with polyolefin.

In Composition (II) of the present invention, the thermoplastic polymer(A) is a polystyrene polymer, the block (b1) is a polystyrene blockwhich has high compatibility with the polystyrene polymer (thermoplasticpolymer (A)) and the block (b2) is a polyolefin block which has highcompatibility with the liquid compound (C), and the block copolymer (B)is at least one selected from the group consisting of apolystyrene-poly(ethylene/propylene) block copolymer (SEP), apolystyrene-poly(ethylene/butylene) block copolymer (SEB), apolystyrene-poly(ethylene/propylene)-polystyrene block copolymer (SEPS),a polystyrene-poly(ethylene/butylene)-polystyrene block copolymer(SEBS), and a polystyrene-poly(ethylene-ethylene/propylene)-polystyreneblock copolymer (SEEPS).

In Composition (II) of the present invention, the liquid compound (C) isan organic compound or organic compound solution which has highercompatibility with polyolefin than with polystyrene and which has lowcompatibility with a polystyrene, such as an alkyl or alkenyl or anester or ether thereof or a polyether amine or alcohol.

In the compositions of the present invention, at least one of apharmaceutical product, an antibacterial agent, an antifungal agent, anantiviral agent, an antistatic agent, an antialgal agent, apreservative, an aromatic agent, an insect repellent, an insecticide, arodent repellent, a bird repellent, an animal repellent, an attractant,an agricultural chemical, an antifouling agent, a flame retardant, adust-capturing agent, a fertilizer and a deodorant can be used for theliquid compound (C).

A molded article of the present invention is formed from Composition(I), (II) or (III). The molded article has a coating of the liquidcompound (C) which has bled out of the composition, the coating having athickness of 1 μm or less.

The molded article of the present invention is an extrusion-moldedarticle formed from Composition (I), (II) or (III). Examples of themolded article include a fiber, a fabric or fiber product made of thefiber and a laminate of the same, a pipe, a sheet, a film, and alaminate molded article of the same.

Examples of the molded article of the present invention include aninjection-molded article, a rotational-molded article, and a blow-moldedarticle each of which is formed from Composition (I), (II) or (III).

The present invention is directed to a paint or coating material formedfrom Composition (I), (II) or (III). The present invention is alsodirected to a filter which includes as a main dust-capturing materialthe fabric, fiber product, or laminate formed from Composition (I), (II)or (III).

The thermoplastic polymer (A) is a polymer or elastomer moldable into afilm, sheet, fiber, extrusion-molded article, etc. Examples of thethermoplastic polymer (A) include a polyolefin polymer, to which aliquid organic polymer is relatively difficult to add with highconcentration. Specific examples of the thermoplastic polymer (A)include homopolymers, such as polyethylene, polypropylene, polystyrene,polyacrylate, polymethacrylate, poly(1-butene), poly(1-pentene) andpolymethylpentene, and copolymers thereof. Among such candidates, thethermoplastic polymer (A) used in the composition of the presentinvention is preferably a polyolefin polymer or polystyrene polymerwhich has a low melting point and low reactivity. Using a high meltingpoint polymer as the thermoplastic polymer (A) would result in a largedifference between the melting point and the boiling point of the liquidcompound added and hence a large loss of the liquid compound in molding,and thus entails use of a special quenching/loss-preventing device, suchas an underwater cutter, for example.

In the compositions of the present invention, the block copolymer (B) isphase-separated from the thermoplastic polymer (A) which constitutes amatrix (hereinafter, sometimes referred to as “matrix polymer (A)”) andis metastably dispersed in the matrix polymer (A) so that the blockcopolymer (B) forms an interface between the matrix polymer (A) and theliquid compound (C). The block copolymer (B) includes at least twopolymer blocks: a block (b1) having high compatibility with the matrixpolymer (A) but low compatibility with the liquid compound (C) and ablock (b2) having high compatibility with the liquid compound (C) andlow compatibility with the matrix polymer (A). In the compositions ofthe present invention, combination of materials used as the matrixpolymer (A), the liquid compound (C) and the block copolymer (B) is akey to formation of a stable liquid-in-solid polymer emulsion.

The composition of the present invention contains 0.1 to 50 parts byweight of the block copolymer (B) relative to 100 parts by weight of thematrix polymer (A). In the case where the content of the block copolymer(B) is less than 0.1 part by weight, the absolute quantity of the liquidcompound (C) contained in the liquid-in-solid polymer emulsion is small.As a result, a product of such a composition cannot have a sufficientfunction. On the other hand, the content of the block copolymer (B) morethan 50 parts by weight is too much to form a desired liquid-in-solidpolymer emulsion. The content of the block copolymer (B) is preferably0.2 to 30 parts by weight relative to 100 parts by weight of the matrixpolymer (A). In the composition, the content of the liquid compound (C)and the content of the block copolymer (B) correlate to each other.

Compositions (I) and (II) of the present invention are also used asmasterbatches. In such cases, the content of the block copolymer (B) ispreferably 4 to 25 parts by weight relative to 100 parts by weight ofthe matrix polymer (A), although it depends on the dilution ratio.Moreover, many of molded articles of the present invention are formedusing a diluted masterbatch. The content of the block copolymer (B) inthe molded product is preferably 0.2 to 2.5 parts by weight relative to100 parts by weight of the matrix polymer (A).

In Composition (I) of the present invention where the matrix polymer (A)is a polyolefin polymer, the block copolymer (B) includes a polyolefinblock as the block (b1) and therefore has excellent compatibility withthe matrix polymer (A). Also, the block copolymer (B) includes apolystyrene block as the block (b2) and therefore has excellentcompatibility with an aromatic or alicyclic compound of the liquidcompound (C). The block copolymer (B) contained in Composition (I) is atleast one selected from the group consisting of apolystyrene-poly(ethylene/propylene) block copolymer (SEP), apolystyrene-poly(ethylene/butylene) block copolymer (SEB), apolystyrene-poly(ethylene/propylene)-polystyrene block copolymer (SEPS),a polystyrene-poly(ethylene/butylene)-polystyrene block copolymer(SEBS), and a polystyrene-poly(ethylene-ethylene/propylene)-polystyreneblock copolymer (SEEPS).

In the molten matrix polymer (A), the block copolymer (B) isphase-separated but metastably dispersed because of high compatibilitywith the matrix polymer (A) of the block (b1) of the block copolymer(B). The block copolymer (B) shows a surfactant-like behavior andconstitutes an interface to form a liquid-in-solid polymer emulsion inwhich the liquid compound (C) having low compatibility with the matrixpolymer (A) is enclosed in the copolymer (B). The emulsion is formed bya membrane of the block copolymer (B). The membrane is formed by twolayers: the outer layer including a block (b1) which has highcompatibility with the polymer (A) and the inner layer including a block(b2) which has high compatibility with the liquid compound (C). Formingsuch a liquid-in-solid polymer emulsion enables a large amount of liquidcompound (C) to be stably contained therein such that it is kept inliquid form.

This liquid-in-solid polymer emulsion form is stably maintained evenafter solidification of the composition. Even after melted and shearedagain in a closed system, the liquid-in-solid polymer emulsion form isre-formed and stably maintained. The liquid compound (C) is enclosed bya dense membrane of the block copolymer (B) such that the permeabilityof the liquid compound (C) through the block copolymer membrane is lowand the liquid compound (C) is locally stored. Thus, this structureprovides excellent sustained-release characteristics.

The liquid compound (C) used in the compositions of the presentinvention which is liquid at 100° C. or lower is preferably selected inview of such a combination with the matrix polymer (A) and the block(b1) of the block copolymer (B) that a stable liquid-in-solid polymeremulsion is formed. In particular, the liquid compound (C) selectedpreferably has low compatibility with and is phase-separated from thematrix polymer (A), but has high compatibility with the block (b1) ofthe block copolymer (B). Examples of the liquid compound (C) include anorganic solution and an aqueous solution. Preferably, the liquidcompound (C) used in Compositions (I) to (III) of the present inventionis an organic solution. The liquid compound (C) is preferably liquid at100° C. or lower, particularly at room temperature, in view of easyselection of a suitable dispersion rate of active components. An organicsolution or aqueous solution wherein an organic compound which is solidat 100° C. or lower or an unmeltable compound, such as an inorganiccompound, is dissolved in a solvent may be used for the presentinvention. Alternatively, using an organic solution of a low boilingpoint organic compound, or the like, ensures a decreased partialpressure and lower release rate.

Examples of the organic compound which is liquid at 100° C. or lower andcan be used as the liquid compound (C) in the compositions of thepresent invention include: a natural essential oil, such as terpenes,and the like; a conifer essential oil, such as cedarwood oil containinga large quantity of thuyopsene with excellent insect repellency and tickrepellency; a peppermint oil containing a large quantity of menthol withexcellent rodent repellency; an eucalyptus oil with excellentantibacterial and antiviral properties and bronchodilatation effect; alemongrass oil with excellent antifungal property; and a lavender oilwith excellent aromatic property. The organic compound with agriculturalchemical effects may be a pyrethroid compound insecticide or herbicide,such as permethrin, or the like. The organic compound with fertilizationeffects may be a low-molecular organic material containing amino acids.The organic compound with attraction effects may be an animal-attractinghormone derived from animals or plants. The organic compound withrepellency may be capsaicin, limonene, or the like, which is repellentto animals. The organic compound with bactericidal effects may betriclosan. The organic compound with antifungal effects may be anisothiazoline compound. The organic compound with antibacterial effectsmay be zinc pyrithione. The preservative may be paraben, EDTA, or thelike. The antistatic agent may be stearyl polyether monoglyceride,stearyl polyether diglyceride, stearyl aminopolyether, or the like.

The sustained release property and sustained release period of thefunctional liquid compound (C) can be controlled based on the amount ofthe liquid compound (C) contained, the compatibility, amount, andinterfacial properties of the matrix polymer (A) and the block copolymer(B), and the ratio between the block copolymer (B) and the liquidcompound (C), i.e., what liquid-in-solid polymer emulsion is formed.

The polymer compositions of the present invention may contain anotheradditive without departing from the spirit of the present invention. Theadditive may be an inorganic filler, a pigment, a lubricant, astabilizer, or the like.

Kneading of the polymer compositions of the present invention may berealized by a general melt-kneading method using a single rotor kneaderwith liquid dispenser or a twin rotor kneader which provides higherkneading efficiency. Alternatively, general extrusion molding, blowmolding, injection molding, and rotational molding with such a machinemay be directly employed.

Since the compositions of the present invention are in the state offinely dispersed emulsion, heating the liquid compound enclosed in theemulsion to its boiling point or higher only produces small expansionenergy per emulsion droplet. Therefore, even at such a high temperaturethat the compositions are molten, expansion is suppressed due to themelt viscosity of the thermoplastic polymer (A) which constitutes thematrix, so that the compositions stay liquid and maintain their kneadedstate. Even if such a system is in a high temperature environment equalto or higher than the atmospheric boiling point of water or aqueoussolution, the emulsion droplets are maintained slightly swollen ascompared with what they are when pressurized but only have small volumesso long as appropriate temperature and viscosity conditions are set inthe system. Thereafter, the emulsion droplets are cooled to atemperature equal to or lower than the atmospheric boiling point to havesmaller volumes along with transition from the pressurized state to thenormal pressure state. As a result, the liquid compound is completelyrestored to liquid. More specifically, as will be described later inExamples, the liquid compound (C) may be mixed in the thermoplasticpolymer (A) to form emulsion at a process temperature equal to or higherthan its atmospheric boiling point, and the resultant mixture may besubjected to an extrusion process.

Compositions (I) and (II) of the present invention may be used asmasterbatches. For example, the composition may be diluted with othermatrix polymer to produce Composition (III). For example, a polymerprocessable at a low melting point, such as LDPE, or the like, may beused as the matrix polymer (A) (thermoplastic polymer (A)) together withthe liquid compound (C) to produce a masterbatch of Composition (I) ofthe present invention. Composition (I) may be diluted with PP which hasa high melting point to produce a finished product. In this case, aliquid-in-solid polymer emulsion composition (Composition (III)) havinga double enclosure structure is formed as follows: islands of the LDPEare formed in the PP, and in the islands the liquid compound (C) isenclosed with the block copolymer (B) so that the liquid-in-solidpolymer emulsion composition is formed, and the droplets of the emulsioncomposition are finely dispersed in the PP. It is also preferred to mix,as necessary, a compatibilizer suitable to stable blending ofComposition (I) and the PP and improvement in strength due to fineblending.

The other matrix polymer used for dilution in the present invention canbe selected from a wide range of candidates so long as stable productionis ensured. With a material other than the above-described two similartypes of polyolefins, for example, PET, a liquid-in-solid polymeremulsion having a double enclosure structure is formed in which islandsof the LDPE are formed in the PET, and in the islands the liquidcompound (C) enclosed by the copolymer (B) is contained; and aliquid-in-solid polymer emulsion having a double enclosure structure isformed in which islands of the LDPE are formed in the PVC, and in theislands the liquid compound (C) enclosed by the copolymer (B) iscontained.

It is difficult to give a polymer composition which includes an aromaticpolymer (e.g., a PET, a polystyrene) or a polymer using an aromaticplasticizer (e.g., a PVC) as the thermoplastic polymer (A) and mix anaromatic liquid compound (C) in the thermoplastic polymer (A) such thata polymer composition in the form of liquid-in-solid polymer emulsionbecause of high compatibility between the thermoplastic polymer (A)which constitutes the matrix and the liquid compound (C). However, thedesired object of the present invention can be achieved by polyblendingthe polymer composition (I) in the form of liquid-in-solid polymeremulsion in which the aromatic liquid compound (C) is dispersed inpolyolefin used as the thermoplastic polymer (A) which constitutes thematrix with a new matrix polymer, an aromatic polymer (e.g., a PET, apolystyrene) or a polymer using an aromatic plasticizer (e.g., apolyvinyl chloride), to form a double-enclosed liquid-in-solid polymeremulsion.

The other matrix polymer may be a polymer precursor. When athermosetting novolak polyphenol resin precursor is used, athermosetting liquid-in-solid polymer emulsion having a double enclosurestructure is formed in which a liquid-in-solid polymer emulsioncontaining the liquid compound (C) enclosed by the copolymer (B) residesinside thermosetting polyphenol resin. Examples of the thermosettingresin used herein include xylene resins, urea resins, epoxy resins,melamine-urea resins, etc.

The other matrix polymer may be temporarily a polymer solution. Forexample, a liquid-in-solid polymer emulsion having a double enclosurestructure is formed which includes a polyurethane liquid-in-solidpolymer emulsion residing inside a polyacrylonitrile DMF solution.

A composition including the thermoplastic polymer (A) which constitutesa matrix, the block copolymer (B) and a biodegradable polymer as theother polymer can be formed into a product which possessesbiodegradability and is therefore suitable to feeding of a long-actingpesticide or fertilizer.

The fiber of the present invention may be a staple, a filament, a tapeyarn, or a short cut fiber, which is manufactured from a fiber producedby melt-spinning the composition of the present invention. The fiber ofthe present invention may be used to manufacture a thermally fusednonwoven fabric, a multilayer laminate, and a meltblown, spunbonded,needle punched, dry, wet, chemical bonded nonwoven fabric. Further, thefabric of the present invention may be a fabric produced by blendspinning, combining filament, yarn doubling, union weaving or unionknitting the fiber of the present invention.

The fiber of the present invention may be used as a filling material forbedclothes or a pillow, a toy such as a doll, an interior textileproduct such as a curtain or a chair cover, and an insect repellant,tick repellant or insecticidal textile product such as a mosquito net, ascreen door or clothes.

The molded article of the present invention may be a molded articleproduced by molding the composition of the present invention with theuse of a common production method, for example, an injection molding, ablow molding, an extrusion molding or a rotational molding, andincludes, for example, a container; a film produced by a commoninflation method or T-die method; a sheet produced by a T-die method; atank produced by a rotational molding; a coating material, a wirecovering material, a laminate or a hose produced by an extrusionmolding; and others.

The paint of the present invention includes a powdered paint including afine particle obtained by freeze crushing the composition of the presentinvention, a paint containing the powdered fine particle, and a paintcontaining the powdered fine particle dissolved or dispersed in asolvent. The thermoplastic polymer (A) or/and the other polymer ispreferably dissolved in the solvent or dispersion medium so that thepaint maintains an appropriate viscosity.

The powdered paint is produced by mixing a pigment and if necessary anadditive such as a surface control agent, a plasticizer, an ultravioletray absorbing agent, an antioxidant, an anti-popping agent, a staticcontrol agent, a curing catalyst, an antiblocking agent or a flowcontrol agent to give a pellet, and pulverizing the pellet. Thepreferred pulverizing method includes a freeze mill or hammerpulverization utilizing a liquid nitrogen, and by such a method, apowder having a mean particle size of 100 μm or less is obtained. Thepainting method may be the above-mentioned common method. The pigmentmay include, for example, iron oxide, lead oxide, carbon black, titaniumdioxide, talc, sulfated barium, cadmium yellow, cadmium red, chromeyellow, aluminum flake, and copper phthalocyanine blue. The pigment isnot limited to these examples. Among these pigments, two or morepigments may be used together. The amount of the pigment blended ispreferably from 0.5 to 40 wt %.

The liquid paint of the present invention is produced by suitablyblending and mixing the powder of the present invention in the samemanner as the pigment. In particular, it is advantageously preferred asa ship's bottom paint to have a large film thickness and a slightroughness on the surface of the paint film because the water disturbancecan become small. The ship's bottom paint of the present inventioncontaining Capsaicin or Cedarwood Virginia oil is effective forinhibiting growth of a fouling such as barnacle. Either component is afood additive, and a safe and eco-friendly component.

The liquid paint composition of the present invention is produced byheat-mixing the above-described paint of the present invention into asolvent for paint, such as toluene, xylene or n-hexane under pressurefor finely dispersing the paint in the solvent in a molten state, andmixing the resulting matter with a thermosetting resin solution to apredetermined concentration to give a liquid paint composition havingthe above-mentioned function for use as a general paint. As comparedwith a conventional method using a microcapsule, a finer and more stablesoft capsule is provided at a low price.

The filter of the present invention includes the fiber structure of thepresent invention having a fiber surface coated with the liquid compound(C) so that the liquid compound (C) forms a thin film having a thicknessof 1 μm or less, and demonstrates a high degree of a fine dustcollection efficiency by a liquid bridging force of the liquid. Dust iscollected on the surface of the thin film by a strong adherence due tothe liquid bridging force of the liquid. In the case of using the fiberstructure as a filter, the structure exerts several tens times higherdegree of the dust collection efficiency than a conventional filterwhile having the high air permeability and the low pressure drop. In thecase of using the fiber structure as a wiping cloth, the structureexerts a performance for efficiently wiping off fine dust.

As a method for forming a thin film of the liquid compound (C) on thesurface of the fiber, there is a method which comprises providing asolution of the organic compound dissolved in a high-volatile solvent,impregnating a fiber structure with the solution, and then volatilizingthe solvent to leave the compound on the surface of the fiber. However,the method requires a great deal of expenses, and needs a complicatedprocess such as the use of an apparatus for recovering a high-volatilesolvent. Therefore, the method is not adequate to a practical industrialproduction. In the case of such finishing, the thin film of the liquidis removed once the fiber is washed, as a result, the effect of theliquid is lost. On the other hand, in the product of the presentinvention, a fresh liquid organic compound bleeds out from the insidethereof even after washing to form a thin film, and the function of theliquid is recovered.

EXAMPLES

Hereinafter, the following examples are intended to describe thisinvention in further detail and should by no means be interpreted asdefining the scope of the invention.

(1) Measurement of Weight and GC

A molded article (molded pellet, fiber, or film) was put in a hot airdryer at 60° C. or 80° C., and the weight of the article was measuredwith time by a DTA-TGA analysis. Based on the weight loss, the amount oflost part of the functional organic compound (liquid compound) from themolded article was determined. In parallel, the concentration of theresidual compound was measured by GC-2010 (manufactured by ShimadzuCorporation) in accordance with the trichlorobenzene hot extractionmethod.

(2) Observation of Emulsion

The surface to be observed was treated with ruthenium tetrachloride tostain an aromatic ring part, and the treated surface was observed by ascanning electron microscope (SEM).

Example 1

85 kg of polypropylene (“Y6005GM” manufactured by Prime Polymer Co.,Ltd.) as the matrix polymer (A) and 10 kg of SEP (“SEP1001” manufacturedby Kuraray Co., Ltd.) as the block copolymer (B) were ordinarily kneadedby a conventional biaxial extruder. While kneaded, the mixture wassupplied with 5 kg of 1,3-diphenylpropane as the liquid compound (C),which was liquid at room temperature, via a plunger pump. The resultantmixture was extruded from the die head at 190° C. in the form of a cord.The cord-like mixture was quenched in water and cut with a cutter, suchthat granular pellets of Composition (I) of the present invention wereproduced.

The DTA-TGA measurement result of the pellets showed that the amount ofresidual 1,3-diphenylpropane was 4.57%, which was an excellent yield.The pellets were then put in a hot air dryer at 80° C. The weight of thepellets was measured before the pellets were put in the dryer and after3 days, 7 days, 14 days, and 30 days. The weight loss was recorded foreach measurement. The weight loss of 1,3-diphenylpropane remained at 72%even after 30 days, which meant good retention of the functional liquid(1,3-diphenylpropane). In view of such an evaluation criterion for tickrepellent efficacy of carpets established by the Interior-fabricsPerformance Evaluation Conference that a facilitated test under 81° C.for 3 days is equivalent to a test under atmospheric temperature for 3years, it is appreciated that the pellets of Example 1 has excellentlong-term effect sustainability. FIG. 1 is a SEM observation image, inwhich sea-islands each having a particle size smaller than 1 μm areobserved, and the inside of the islands is hollow as seen through somecorrupted islands. The cavity is a trace of evaporation of1,3-diphenylpropane liquid from the inside of the membrane-rupturedisland because of SEM observation carried out in vacuum and clearlyindicates that a liquid-in-solid polymer emulsion structure was formed.

Example 2

85 kg of LLDPE polymer (“NOVATEC LL” manufactured by Japan PolyethyleneCorporation) as the matrix polymer (A) and 10 kg of SEPS (“SEPS2002”manufactured by Kuraray Co., Ltd.) as the block copolymer (B) wereordinarily kneaded by a conventional biaxial extruder. While kneaded,the mixture was supplied with 5 kg of Cedarwood oil havingantibacterial, antifungal and insect-repellent effects as the liquidcompound (C) via a plunger pump. The resultant mixture was extruded fromthe die head at 160° C. in the form of a cord. The cord-like mixture wasquenched in water and cut with a cutter, such that granular pellets ofComposition (I) of the present invention were produced. The DTA-TGAmeasurement result of the pellets showed that the amount of residualCedarwood oil was 4.62%, which was an excellent yield. The pellets werethen put in a dryer at 80° C. The weight of the pellets was measuredbefore the pellets were put in the dryer and after 7 days. The weightloss was recorded for each measurement. The weight loss of Cedarwood oilremained at 46% even after 7 days, which meant good retention of thefunctional liquid (Cedarwood oil). FIG. 2 is a SEM observation image, inwhich islands smaller than those observed in FIG. 1 are observed, andthe inside of the islands is hollow as seen through some corruptedislands. It is appreciated from comparison with Example 1 that theliquid-in-solid polymer emulsion structure depends on the matrix polymer(A), the block copolymer (B) and the liquid compound (C).

Example 3

As in Example 2, 85 kg of LLDPE polymer (“NOVATEC LL” manufactured byJapan Polyethylene Corporation) as the matrix polymer (A) and 15 kg ofSEPS (“SEPS2002” manufactured by Kuraray Co., Ltd.) as the blockcopolymer (B) were ordinarily kneaded by a conventional biaxialextruder. While kneaded, the mixture was supplied with 5 kg ofPeppermint oil as the liquid compound (C) via a plunger pump. Theresultant mixture was extruded from the die head at 160° C. in the formof a cord. The cord-like mixture was quenched in water and cut with acutter, such that granular pellets of Composition (I) of the presentinvention were produced. The DTA-TGA measurement result of thePeppermint oil itself while the temperature was gradually increased fromroom temperature showed that the weight of the Peppermint oil was almostlost before 156° C. On the other hand, the DTA-TGA measurement result ofthe pellets of Example 3 showed that the amount of residual Peppermintoil was 4.42%, which was an excellent yield even though the temperatureof the die head was higher than the evaporation temperature of thePeppermint oil. The pellets were then put in a dryer at 80° C. Theweight of the pellets was measured before the pellets were put in thedryer and after 7 days. The weight loss was recorded for eachmeasurement. The weight loss of Peppermint oil remained at 53% evenafter 7 days, which meant good retention of the functional liquid(Peppermint oil). FIG. 3 is a SEM observation image, in which islandsgreater than those observed in FIG. 2 are observed, and the inside ofthe islands is hollow as seen through some corrupted islands. It isappreciated that the liquid-in-solid polymer emulsion structure dependson the liquid compound (C) even though the matrix polymer (A) and theblock copolymer (B) are the same.

Example 4

As in Example 2, 85 kg of LLDPE polymer (“NOVATEC LL” manufactured byJapan Polyethylene Corporation) as the matrix polymer (A) and 10 kg ofSEPS (“SEPS2002” manufactured by Kuraray Co., Ltd.) as the blockcopolymer (B) were ordinarily kneaded by a conventional biaxialextruder. While kneaded, the mixture was supplied with 5 kg ofEucalyptus oil as the liquid compound (C) via a plunger pump. Theresultant mixture was extruded from the die head at 160° C. in the formof a cord. The cord-like mixture was quenched in water and cut with acutter, such that granular pellets of Composition (I) of the presentinvention were produced. The DTA-TGA measurement result of the pelletsshowed that the amount of residual Eucalyptus oil was 4.58%, which wasan excellent yield.

Comparative Example 1

The conditions for Comparative Example 1 were basically the same asthose of Example 1 except that the block copolymer (B) was not added.Specifically, while 100 kg of polypropylene (“Y6005GM” manufactured byPrime Polymer Co., Ltd.) was ordinarily kneaded by a conventionalbiaxial extruder, 5 kg of 1,3-diphenylpropane was added thereto via aplunger pump. The resultant mixture was extruded from the die head inthe form of a cord. The cord-like mixture was quenched in water and cutwith a cutter, such that granular pellets of the comparative compositionwere produced. A phase-separated portion of 1,3-diphenylpropane burstfrom the die head, and the resultant pellets were soaked in a largeamount of 1,3-diphenylpropane that has bled out. Therefore, the pelletswere aggregated together and were not usable for the next step.

Example 5

As in Example 2, 85 kg of LLDPE polymer (“NOVATEC LL” manufactured byJapan Polyethylene Corporation) as the matrix polymer (A) and 15 kg ofSEPS (“SEPS2002” manufactured by Kuraray Co., Ltd.) as the blockcopolymer (B) were ordinarily kneaded by a conventional biaxialextruder. While kneaded, the mixture was supplied with 5 kg ofinsecticide Permethrin as the liquid compound (C) via a plunger pump.The resultant mixture was extruded from the die head at 160° C. in theform of a cord. The cord-like mixture was quenched in water and cut witha cutter, such that granular pellets of Composition (I) of the presentinvention were produced. The GC measurement result of the pellets showedthat the amount of residual Permethrin was 4.68%, which was an excellentyield.

Example 6

10 parts by weight of the pellets (masterbatch) prepared in Example 5and 90 parts by weight of PP pellets were mixed and subjected to aspin-draw melt-spinning process at the spinning temperature of 230° C.,such that PP multifilaments of 110 dTex/24 F were produced. The GCmeasurement result of the filaments showed that the amount of residualPermethrin was 0.37%, which was an excellent yield, even though thefilaments were heated twice. The filaments also exhibited excellentmechanical properties: the tensile strength of 4.2 g/dTex and thetensile elongation of 70%. The filaments were knitted into a tricotmosquito net fabric of the present invention. The fabric exhibited suchan excellent knockdown effect that 50% knockdown time of mosquitoes(Culex pipiens) based on the WHO kit method was 16 minutes. FIG. 4 is across-sectional SEM observation image of the multifilament of Example 6,in which fine sea-islands are observed, and it is confirmed that theliquid-in-solid polymer emulsion structure was re-formed after there-melting/re-spinning process.

Example 7

10 parts by weight of the pellets (masterbatch) prepared in Example 2and 90 parts by weight of PP pellets were mixed and subjected to acommon melt-spinning process, such that PP BCF multifilaments of 1650dtex/96 F were produced. The GC measurement result of the filamentsshowed that the amount of residual Cedarwood oil was 0.36%, which was anexcellent yield, even though the filaments were heated twice. The BCFmultifilaments were used to manufacture a loop pile tufted carpet of 1kg/m². The manufacture of the carpet included the third heating processof baking a backing material. The carpet exhibited 86% repellency toDermatophagoides farinae, which means excellent repellency to ticks.

Example 8

20 parts by weight of the pellets (masterbatch) prepared in Example 3and 80 parts by weight of HDPE pellets were mixed and subjected to acommon T-die process at the die temperature of 190° C. to produce afilm. The film was slit to produce a tape yarn of 1450 dTex. The GCmeasurement result of the tape yarn showed that the amount of residualPeppermint oil was 0.36%, which was an excellent yield. The tape yarnwas used as warp and a common HDPE tape yarn was used as weft tofabricate a plane circular-woven hessian fabric. A rat food was wrappedin the hessian fabric and placed in a breeding cage of rats. For 5Rattus norvegicus caraco of 17-week-old, whether or not they had eatenthe food was checked after 3 days and nights. Before the end of thefirst day, no rats ate the food. Before the end of the second day, onlytwo rats ate the food. This result means that the fabric exhibitedexcellent rodent repellency. As for a blank sample placed in the samecage, 3 rats ate the food before the end of the first day, and the foodwere all eaten before the end of the second day.

Example 9

10 parts by weight of the pellets (masterbatch) prepared in Example 1and 10 parts by weight of polypropylene (“Y6005GM” manufactured by PrimePolymer Co., Ltd.) were mixed and subjected to common melt-extrusion andmelt-blowing processes to produce a meltblown nonwoven fabric filterhaving a weight of 22 g/cm². The resultant fabric was subjected to aquartz dust collection efficiency test (test conditions: quartz dusthaving a particle size of 1.0 μm; wind velocity of 8.6 cm/second). Theresult of the test indicated that the dust collection efficiency of themeltblown nonwoven fabric was about twice as high as that of a commonmeltblown nonwoven fabric with the same level of pressure loss (about 16Pa).

Example 10

85 kg of polystyrene (“GPPS679” manufactured by PS Japan Corporation) asthe matrix polymer (A) and 10 kg of SEP (“SEP2014” manufactured byKuraray Co., Ltd.) as the block copolymer (B) were ordinarily kneaded bya conventional biaxial extruder. While kneaded, the mixture was suppliedwith 5 kg of antistatic agent, polyoxyethylene stearylamine, as theliquid compound (C) via a plunger pump. The resultant mixture wasextruded from the die head at 190° C. in the form of a cord. Thecord-like mixture was quenched in water and cut with a cutter, such thatgranular pellets of Composition (II) of the present invention wereproduced. The DTA-TGA measurement result of the pellets showed that theamount of residual polyoxyethylene stearylamine was 4.67%, which was anexcellent yield. The pellets (masterbatch) were diluted tenfold withLDPE (E), and an inflation film was produced from the dilution by acommon method. The surface resistance of the film was measured accordingto JIS K 6911 under the following conditions: applied voltage of 500 V;20° C.; and 40% RH. The result was 1.2×10¹¹Ω, which means sufficientanti-dust adhesion as compared with a blank sample whose result was2.5×10¹⁵Ω.

Example 11

40 parts by weight of the pellets (masterbatch) prepared in Example 2,30 parts by weight of polyvinyl chloride powder having a molecularweight of about 2000, and 30 parts by weight of plasticizer,1,2-di-2-ethylhexyl phthalate (hereinafter, referred to as “DOP”), werekneaded at 140° C. by a biaxial extruder. The resultant mixture wasextruded from the die head in the form of a cord. The cord-like mixturewas quenched in water and cut with a cutter, such that soft polyvinylchloride pellets of Composition (III) of the present invention, in whichLDPE polymer composition was polyblended, were produced. The surface ofthe pellets were obviously a dry-touch surface, and bleeding out of theCedarwood oil was not recognized in appearance. The amount of residualCedarwood oil in the pellets was 1.83% by weight, which was a highyield. FIG. 5 is a cross-sectional SEM observation image of the pelletsof Example 11, in which fine sea-islands are observed, and it isconfirmed that the liquid-in-solid polymer emulsion structure wasre-formed after the re-melting process to form a double enclosurestructure even though a large amount of DPO which is highly compatiblewith Cedarwood oil was contained in the matrix polymer.

Example 12

The pellets (masterbatch) prepared in Example 11 were diluted fourfoldwith polyvinyl chloride and plasticizer DOP of equal amounts, and aninflation film having a thickness of 60 μm and a width of 2 m wasproduced from the dilution by a common inflation film method. Thesurface of the film was obviously a dry-touch surface, and bleeding outof the Cedarwood oil was not recognized in appearance. The amount ofresidual Cedarwood oil in the pellets was 0.37% by weight, which was ahigh yield.

Example 13

10 parts by weight of the pellets (masterbatch) prepared in Example 2and 90 parts by weight of dried PET pellets having an IV value of 0.70were mixed and melted by a mixer/extruder. The mixture was measured by agear pump and spun according to a spin-draw method at a die temperatureof 270° C. to produce multifilaments of 165 dTex/48 F. The amount ofresidual Cedarwood oil in the filaments was 0.41% by weight, which was ahigh yield. The filaments were dyed in black according to a commonhigh-pressure dyeing method. The dyed filaments were subjected to anantibacterial test according to JIS L1902 bacterial suspensionabsorption method. The test result was such that the value ofbacteriostatic activity to Staphylococcus aureus was 2.8, which meansexcellent antibacterial effect.

Example 14

20 kg of the pellets (masterbatch) prepared in Example 2 and 80 kg ofLDPE containing 50% by weight of titanium oxide were mixed, to which anadequate amount of a suitable additive was ordinarily added. The mixturewas kneaded by biaxial extruder. The resultant mixture was extruded fromthe die head in the form of a cord. The cord-like mixture was cooled andcut with a cutter into pellets. The pellets were pulverized while cooledwith liquid nitrogen such that white powdered paint having a meanparticle size of 63 micrometers was produced. The GC measurement resultof the powdered paint showed that the amount of residual Cedarwood oilwas 1.09%, which was an excellent yield. The powdered paint was appliedby electrostatic spraying over a clean iron plate (2 mm thick;width×length=10 cm×20 cm) pretreated with zinc phosphate. The iron platewas heated to 200° C. for 10 minutes to form a coating of 30 μm thick.The coating adhered firmly to the iron plate, which was sufficientcoating strength for practical use. The iron plate was subjected to anantifungal test in accordance with JIS Z2911 2000 wet process withmixture of four types of fungi. The result of the test was such thatgrowth of hypha was not detected in an area inoculated with the fungieven after two weeks.

Example 15

10% by weight of the powdered paint prepared in Example 14 was mixed ina commercially-available water base paint (general-purpose aqueous EGmanufactured by Kansai Paint Co., Ltd.) by a mixer. The viscosity of themixture was adjusted with water to prepare a liquid paint. The paint wascoated over a piece of wood to form a coating of 100 gr/m² thick. Thecoated wood piece was dried and subjected to a antifungal test inaccordance with JIS Z2911 2000 wet process with mixture of four types offungi. The result of the test was such that growth of hypha was notdetected in an area inoculated with the fungi even after two weeks.

1. A composition which constitutes a liquid-in-solid polymer emulsion atroom temperature, comprising: a thermoplastic polymer (A); 0.1 to 50parts by weight of a block copolymer (B) mixed with 100 parts by weightof the thermoplastic polymer (A), the block copolymer (B) beingphase-separated from the thermoplastic polymer (A); and 0.1 to 20 partsby weight of a liquid compound (C) dispersed in 100 parts by weight ofthe mixture of the thermoplastic polymer (A) and the block copolymer(B), wherein the block copolymer (B) contains a block (b1) having highcompatibility with the thermoplastic polymer (A) but low compatibilitywith the liquid compound (C) and a block (b2) having high compatibilitywith the liquid compound (C) but low compatibility with thethermoplastic polymer (A), the liquid compound (C) has low compatibilitywith the block (b1) and the thermoplastic polymer (A) but highcompatibility with the block (b2), the liquid compound (C) beingphase-separated from the thermoplastic polymer (A) and being liquid at100° C. or lower, the liquid compound (C) is enclosed by the blockcopolymer (B) by a surfactant-like function of the block copolymer (B),the thermoplastic polymer (A) is a polystyrene polymer, the block (b1)is a polystyrene block and the block (b2) is a polyolefin block, and theblock copolymer (B) is at least one selected from the group consistingof a polystyrene-poly(ethylene/propylene) block copolymer, apolystyrene-poly(ethylene/butylene) block copolymer, apolystyrene-poly(ethylene/propylene)-polystyrene block copolymer, apolystyrene-poly(ethylene/butylene)-polystyrene block copolymer, and apolystyrene-poly(ethylene-ethylene/propylene)-polystyrene blockcopolymer.
 2. The composition of claim 1, wherein the liquid compound(C) is an organic compound or organic compound solution.
 3. Thecomposition of claim 1, wherein the liquid compound (C) is an organiccompound or organic compound solution which has higher compatibilitywith polyolefin than with polystyrene and which is phase-separated frompolystyrene.
 4. A composition, comprising: a dispersion medium; and thecomposition of claim 1 constituting a liquid-in-solid polymer emulsionat room temperature which is dispersed in the dispersion medium, whereinthe dispersion medium is any one of a polymer other than thethermoplastic polymer (A), a blend of the polymer other than thethermoplastic polymer (A) and a plasticizer, and a solution of thepolymer other than the thermoplastic polymer (A).
 5. The composition ofclaim 4, wherein the polymer other than the thermoplastic polymer (A) isa thermoplastic polymer and/or a thermosetting polymer or thermosettingpolymer precursor.
 6. The composition of claim 1, wherein the liquidcompound (C) is at least one of a pharmaceutical product, anantibacterial agent, an antifungal agent, an antiviral agent, anantistatic agent, an antialgal agent, a preservative, an aromatic agent,an insect repellent, an insecticide, a rodent repellent, a birdrepellent, an animal repellent, an attractant, an agricultural chemical,an antifouling agent, a flame retardant, a dust-capturing agent, afertilizer and a deodorant.
 7. A molded article formed from thecomposition of claim 1, wherein the molded article has a coating of theliquid compound (C) which has bled out of the composition, the coatinghaving a thickness of 1 μm or less.
 8. The molded article of claim 7which is an extrusion-molded article.
 9. The molded article of claim 7which is a fiber, a fabric or fiber product made of the fiber, or alaminate of the same.
 10. The molded article of claim 7 which is a pipe,a sheet, a film, and a laminate of the same.
 11. The molded article ofclaim 7 which is an injection-molded article, a rotational-moldedarticle, or a blow-molded article.
 12. A paint or coating material,comprising the composition of claim 1 or a mixture or dilution of thesame.
 13. A filter, comprising the fabric or fiber product or thelaminate of claim 9 as a main dust-capturing material.